Dyestuffs of the anthraquinone series



Patented Mar. 4 1941 UNITED STATES 2,233,496 PATENT OFFICE (DYESTUFFS OF THE ANTHRAQUINONE SERIES Frederic Bennett Stilmar, Woodstown, N. J., as-

isignor toE. I.-'du Pont deNemours & Company, Wilmington Del., a corporation ofDelaware No Drawing. Application Mayll), 1939, Serial No. 272,775

6 Claims.

This invention relates to the preparation of new and-valuable dyestuffs of the anthraquinone series. The invention relates more particularly to the preparationiof new dyestuffs by the condensation of the new thiophenanthrone carboxylic acids of 'mycopending application, Serial No. 264,125, filed March 25, 1939, with aminoanthraquinone compounds.

In my copending application above mentioned, I have described the preparation of new dyestufi intermediates of 1,9-thiophenanthrone-2- carboxylic acid of the general formula in which R stands for a radical of the class consisting of alkyl radicals containing' 'from 1 to carbon atoms and radicals of the benzene series. These compounds are prepared by condensing l-mercapto-2-anthraquinone carboxylic acid disodium salt with alpha halogen ketones of the general formula in which X stands 'for halogen, and R. has the same significance as above. -As stated in that application, these new .thiophenan'throne carboxylic acid derivatives are valuable in thepreparation of acidylaminoanthraquinone dyestuffs of modified shades in the yellow-to red range of enhanced brightness and good fastness properties.

The present invention is directed to the condensation of the new l,9-thiophenanthrone 2- carboxylic acid compounds-of U. S. application 264,125 with aminoanthraquinones giving dyestuffs having the following general formula in which Aq stands for a radical of an anthraquinone compound and R has the same significance as above. In preparing these compounds the acid chloride of the thiophenanthrone carboxylic: acid :is heated. inanzorganic solventitogether with the amino anthraquinone compound at a temperature from 100 to 200-'C. The dyestuff is filtered off, washed and dried. It is obtained in good-yields-and is of high purity.

The following examples are givento illustrate the invention. The parts used are by Weight.

Example 1 17 parts of C-acetyl-1,9-thiophenanthrone-2- carbonyl chloride and 16.3 parts 1-amino-5-benzoyl-aminoanthraquinone are suspended in 340 parts nitrobenzene. The mixture is heated with agitation to 130135 C. for one and one-half hours. The product, as fine needles, is filtered off and washed with nitrobenzene and finally alcohol.

This dyestuff gives remarkably bright yellow shades of good fastness'on cotton from a redbrown vat. The product dissolves in concentrated sulfuric acidwith a brownish-red coloration. It is represented by the formula:

l AUG-IFH Example- 2 Example 3 12.4 parts of C-acetyl-1,9-thiophenanthrone- Z-carbonyl chloride and 113 parts of 1-amino-4- benzoylamino-anthraquinone are suspended in 310 parts nitrobenzene. hours at -135" C. with agitation, the reaction mixture is filtered. The product, as red needles, is washed with nitrobenzene and alcohol. j

It vdyes cotton brownish-orange shades from a brown vat. The product dissolves in sulfuric acid with a brownish-red coloration. Theformula'is':

Example 4 21.4 parts of C-acetyl-1,9-thiophenanthrone- Z-carbonylchloride and 7.1 parts of 1,5-diaminoanthraquinone are suspended in 350 parts nitrobenzene. :The mixture is heated to -180 C. and held for two hours with agitation. The product isfiltered out, and washed with nitrobenzene and finally alcohol.

The product dyes cotton fast bright reddishyellow shades from a brown vat. It dissolves in concentrated sulfuric acid with a yellowish-red color. The formula is: l

14 parts of C-acetyl-1,9-thiophenanthrone-2- carbonyl chloride and 23.6 parts ;,of l-amino- 5(2:1(N) anthraquinonebenzacridone 2' carbonyl) -aminoanthraquinone are suspended in 600 parts of trichlorobenzene. The reaction mixture is heated with agitation to 205-210 C. and held for two hours. The product is filtered ofi and washed with trichlorobenzene, benzene and alcohol in turns.

It dyes cotton fast yellowish-orange shades from a dull brownish-violet colored vat. The

After heating for two r product dissolves in concentrated sulfuric acid with a yellowish-red color, and has the formula:

. g o Ezrampled I 11.8 parts of C-propionyl LQ-thidphenah- L thrOne-Z-carbonyl chloride: and "11.4. parts of 1-amino-5-benzoylaminoanthraquinone are s'uspended in 250 parts nitrobenzene. After heating for two hours at 130-135 C. the product is filtered off and washed with nitrobenzene and alcohol.

The product dyes cotton very bright yellow shades of good fastness'from a red-brown vat. It dissolves in concentrated sulfuric acid with a brownish-red color. It has the formula:

fl '7y I 11 parts of" Cfloenzoyl- LQ thiophenanthrQ-ne-' 2 carbony1 chloride and 11.4 partsof l-amino-i 5-benzoylaminoanthraquinone were suspended in 300 parts of nitrobenzene. After heating for an hour at 130-135" C-.,the crystalline product is filtered off and washed with nitrobenzene and alcohol.

Theproduct dyes cotton very. brightyellow shades of good fastness from a reddish-brown colored vat. It dissolves in concentrated sul-' furic acid with abrownish-redcolor. It hast-he formula:

N trampled-ff" 1 if 17' parts of C-benzoy1-1}9 thiophehanthrone 75 carbonyl "chloride and 10.3 parts of 1-a'mino-6 chloroanthraquinone 1 are suspended: in 270 parts of nitrolbenzene. LAfter heating an hour at 1'30-135 C. the crystalline :product is'filtered ofi and washed with nitrobenzeneand alcohol.

It dyes cotton fast and brightigreenish-yellow shades from a reddish-brown :colored vat. It dissolves in concentrated sulfuric acid with a yellowish-red color and has the formula C-NH g Example 9 14 parts of C-benzo-yl-1,9-thiophenanthrone-2- carbonyl chloride and 11.4 parts of l-amino-lbenzoylaminoanthraquinone are suspended in 250 parts nitrobenzene. The mixture is heated to -135 and held for one hour. The product is filtered off and. washed with nitrobenzene and alcohol. It dyes cotton orange shades from a brown colored vat, and dissolves'in sulfuric acid with a reddish color. It has the formula:

in which R stands for a substituent of the group consisting of alkyl radicals containing from 1 to 5 carbon atoms and aryl radicals of the benzene series containing not more than one benzene ring, said radicals being attached to the carbonyl radical directly thru carbon to carbon linkages, and Aq stands for a radicalof an anthraquinone compound.

2. The new dyestuffs of the following general formula in which X stands for an alkyl radical of from 1 to 5 carbon atoms which are attached to the carbonyl radical directly thru carbon to carbon linkages, and Aq stands for a radical of an anthraquinone compound.

3. The dyestuff of the formula 4. The dyestufi of the formula 5. The dyestuff of the formula Agile O Y 6. The new dyestufis of the following general in which Y stands for an aryl radical of the formula: V benzene series which contains not morethan one benzene ring and which is attached tothe: ll carbonyl vradical directly thru carbon to carbon f" rings,- and. Aq stands for a radical of an anthra-. 5

quinone compouncLi I FREDERIC BENNETT STILMAR. 

